Azo dyestuffs and process of producing same



Patented Sept. 7, 1937 Azo mznsrnrrs AND PROCESS or PRO- nnome SAME Hans Krzilralla and Paul Garbsch, Ludwigsassignors to York, N.

hafenon-the-Rhine,

General Aniline Works, 1110., New

Germany,

a corporation of Delaware No Drawing. Application Claims.

The present invention relates to azo dyestuffs and aprocess of producing same.

We have found that.

valuable azo obtained by coupling aromatic diazo compounds with N-cycloheXyl-arylamines which are capable of being coupled and which may one or both rings and which have radicle containing be substituted in an aliphatic at least one oxygen atom attached to the connecting nitrogen atom and by so 1 selecting the starting materials that the dyestuffs obained are free from sulphonic and carboxylic acid groups. necting nitrogen The radicle attached to the conatom may be for example a hydroxyethyl, hydroxypropyl or dihydroxypropyl radicle or a hydroxyethyl allryl or hydroxyalkyl ether or hydroxyethyl ester radicle.

The new dyestuffs are eminently suitable for dyeing cellulose esters and ethers. They may also be used for dyeing or artificial compositi hydrocarbons, such as benzene or paraffin wax, fats, such as palmitin or stearin,

ons. By reason of their good solubility in organic solvents, they are also suitable for the preparation of colored spirit or cellulose ester lacquers. good fastness to. sublimation and may therefore serve especially advantageously for the preparaand intaglio printing inks.

tion of double-tone The dyestuffs have a The following examples will further illustrate how the present invention is carried out in practice but the invention examples.

is not restricted to these The parts are byweight.

Example 1 The diazo compound derived from 139 parts of l-amino-d-nitrobenzene is coupled with 232 parts of N hydroxyethyl N cyclohexylaminobenzene which are dissolved in 5000 parts of water and 150 parts of concentrated hydrochloric acid. A dyestufi is obtained which'dyes acetate artificial silk 401 orange: shades.

1 Errample 2 The diazo compound derived from 1'73 parts of 1-amino-2-chlorl-nitrobenzene is coupled with a solution of 232 parts of N-hydroxyethyl-N-cyclohexylaminobenzene in 5000 parts of water and 150 parts of concentrated hydrochloric acid. The dyestuff obtained colors nitrocellulose ester lacquers red shades.

mess to sublimation, it is for use in double-tone The dyestuff may By reason of its good fastalso eminently suitable and intaglio printing inks.

be dissolved in benzene and treated with acetic acid anhydride. The acylated dyestuff thus obtained colors nitrocellulose ester lacquers red shades.

tained if N-aceto-hydr The same dyestuff is oboxyethylcyclohexy1amino dyestuffs are (ill. 260--96) June 24, 1936, Se. In Germany July 19, 1935 benzene be used instead of N-hydroxyethyl-cyclo hexyl-amino-benzene.

Example 3 The diazo compound derived from 214 parts of lamino-2,5-dichlori-nitrobenzene is poured onto ice and there 232 parts of is added thereto a solution of aminobenzene in 5000 parts of water and parts of concentrated hydrochloric acid. The dyestuff thus obtained colors nitrocellulose ester lacquers red shades and does not tend to sublime and blot in double-tone printing.

If the diazo compound 2.6--dichlorimitrobenzene derived from l-aminobe employed, a dyestuff is obtained having similar properties but a slightly more yellow shade of color.

The diazo solution derived Example 4 from 188 parts of l-amino-2,4-dinitrobenzene is coupled with a solution of 232parts of N-hydroxyethyl-N-cyclohexylaininobenzene in 5000 parts of water and 150 parts of concentrated hydrochloric acid. The

resulting dyestufi lacquers Bordeaux for the preparation of double-tone and intaglio printing inks.

nitrocellulose ester It is also suitable colors red shades.

By using 1-amino-2,4,6-trichlorbenzene, a dyestuff is obtained which colors nitrocellulose ester lacquers yellow shades.

Similar dyestuffs which yield in nitrocellulose ester lacquers colors which lie throughout in the red region are obtained for diazo compound of any of the following compounds: ethyl-cyclohexyl-lexample from the l-amino--nitrobenzene with N-hydroxyamino-2-methylbenzene, N-

hydroXyethyl-cyclohexyl-l-methyl 3 amino -4\- methoxybenzene,

the addition compounds derived frorn 2,3 or more molecular proportions of ethylene oxide and 1 molecular proportion of N-cyclo hexylaminobenzene,

or N-hydroXyethyl-cyclohexyll -aminonaphtha1ene.

Example 5 The diazo solution derived from 139 parts of 1-amino-4nitrobenzene is coupled with a solution of 260 parts of N-ethoxyethyl-cyclohexylaminobenzene (corresponding to the formula in 1500 parts of methanol. The dyestuif obtained dyes acetate artificial silk reddish orange shades. It is also suitable for coloring nitrocellulose ester lacquers.

What We claim is:

1. A process for the production of azo dyestuffs which consists in coupling aromatic diazo compounds with N-cyclohexylarylamines which arylamines are selected from the group consisting of radicle containing at least one oxygen atom at- 2. Azo dyestuffs free boxylic acid groups corresponding to the general formula AN=N-B wherein A stands for an aryl radicle and B for the radicle of an N-cyclohexylarylamine which arylfrom the group consisting of the capable of being radicle containing at least one oxygen atom at- 3. Azo dyestufis free from sulphonic and carboxylic acid groups corresponding to the general formula wherein A stands for a radicle of the benzene series and B for the radicle of an N -cyclohexylarylamine Which arylamine is selected from the group conbenzene and napthameans of at least one CH2-group.

4. Azo dyestuifs free from sulphonic and carboxylic acid groups corresponding to the general formula wherein A stands for a radicle of the benzene series and B for the radicle of an N-cyclohexylarylamine which arylamine is selected from the group consisting of the amines of the benzene and napthalene series capable of being coupled which has an aliphatic radicle of the general formula wherein it stands for a whole number, attached to the connecting nitrogen atom. 5. Azo dyestuifs free from sulphonic and carboxylic acid groups corresponding to the general formula wherein A stands for a radicle of the benzene series and B for the radicle of an N-cyclohexylaminobenzene capable of being coupled which has an aliphatic radicle of the general formula wherein n stands for a whole number, attached to the connecting nitrogen atom.

6. Azo dyestufis free from sulphonic and carboxylic acid groups corresponding to the general (om-c1120 ..11 wherein A stands for a radicle of the benzene series and TL stands for a whole number.

'7. Azo dyestuifs free from sulphonic and carboxylic acid groups corresponding to the general formula wherein A stands for a radicle of the benzene series.

8. The azo dyestuif of the formula 

